US5084293A - Activated ascorbic acid antioxidant compositions and carotenoids, fats, and foods stabilized therewith - Google Patents

Activated ascorbic acid antioxidant compositions and carotenoids, fats, and foods stabilized therewith Download PDF

Info

Publication number
US5084293A
US5084293A US07/544,248 US54424890A US5084293A US 5084293 A US5084293 A US 5084293A US 54424890 A US54424890 A US 54424890A US 5084293 A US5084293 A US 5084293A
Authority
US
United States
Prior art keywords
product
ascorbic acid
activated
antioxidant
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US07/544,248
Other languages
English (en)
Inventor
Paul H. Todd, Jr.
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kalamazoo Holdings Inc
Original Assignee
Kalamazoo Holdings Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kalamazoo Holdings Inc filed Critical Kalamazoo Holdings Inc
Priority to US07/544,248 priority Critical patent/US5084293A/en
Assigned to KALAMAZOO HOLDINGS, INC., A CORP. OF MI reassignment KALAMAZOO HOLDINGS, INC., A CORP. OF MI ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: TODD, PAUL H. JR.
Priority to AT91912368T priority patent/ATE122855T1/de
Priority to PCT/US1991/004503 priority patent/WO1992000019A1/en
Priority to EP91912368A priority patent/EP0536257B1/de
Priority to JP3511949A priority patent/JPH05509115A/ja
Priority to DE69110045T priority patent/DE69110045T2/de
Priority to CA002045416A priority patent/CA2045416A1/en
Priority to IE220591A priority patent/IE912205A1/en
Publication of US5084293A publication Critical patent/US5084293A/en
Application granted granted Critical
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23G—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
    • A23G4/00—Chewing gum
    • A23G4/06—Chewing gum characterised by the composition containing organic or inorganic compounds
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
    • A23K30/00—Processes specially adapted for preservation of materials in order to produce animal feeding-stuffs
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
    • A23L3/34—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
    • A23L3/3454—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of liquids or solids
    • A23L3/3463—Organic compounds; Microorganisms; Enzymes
    • A23L3/3472—Compounds of undetermined constitution obtained from animals or plants
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
    • A23L3/34—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
    • A23L3/3454—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of liquids or solids
    • A23L3/3463—Organic compounds; Microorganisms; Enzymes
    • A23L3/3481—Organic compounds containing oxygen
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
    • A23L3/34—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
    • A23L3/3454—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of liquids or solids
    • A23L3/3463—Organic compounds; Microorganisms; Enzymes
    • A23L3/3481—Organic compounds containing oxygen
    • A23L3/3499—Organic compounds containing oxygen with doubly-bound oxygen
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
    • A23L3/34—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
    • A23L3/3454—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of liquids or solids
    • A23L3/3463—Organic compounds; Microorganisms; Enzymes
    • A23L3/3481—Organic compounds containing oxygen
    • A23L3/3508—Organic compounds containing oxygen containing carboxyl groups
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
    • A23L3/34—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
    • A23L3/3454—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of liquids or solids
    • A23L3/3463—Organic compounds; Microorganisms; Enzymes
    • A23L3/3544—Organic compounds containing hetero rings
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B5/00—Preserving by using additives, e.g. anti-oxidants
    • C11B5/0021—Preserving by using additives, e.g. anti-oxidants containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B5/00—Preserving by using additives, e.g. anti-oxidants
    • C11B5/0092—Mixtures

Definitions

  • Oxidation of fats, oils, flavorings, and carotenoids is well known to degrade these substances, reducing the biological activity of vitamins or provitamins they may contain, diminishing their color stability, creating undesirable flavors and aromas, and also creating various oxidized forms thereof, especially of fats, which are considered to be injurious to health.
  • Inhibition of this oxidation process is normally accomplished commercially be the addition of synthetic antioxidants. These are adapted to the particular substrate, e.g., fat, oil, carotenoid, or flavoring, by the user prior to its incorporation into food. A primary reason for not incorporating the antioxidant earlier is the requirement that the antioxidant be selected for the particular substrate--food to be stabilized. Specific antioxidants are not generally adapted to be incorporated into all foods.
  • Synthetic antioxidants have played, and continue to play, the most important role in substrate stabilization.
  • these are propyl gallate, butylated hydroxyanisole, butylated hydroxy toluene, tertiary butylated hydroxy quinone (which is not permitted for use in the EEC or Japan), and fatty acid esters of ascorbic acid, such as ascorbyl palmitate.
  • fatty acid esters of ascorbic acid such as ascorbyl palmitate.
  • rosemary extracts and tocopherols are most importance in this category.
  • the oxidative process begins immediately upon completion of the refining of the substrate, and it is most efficacious to introduce the antioxidant immediately upon completion of refining. This prevents the formation of oxidation promoters, which are the first step in the oxidative process. Addition of antioxidants hours or days after refining is much less effective, since the initiators propagate themselves, and the antioxidant dosage must be much greater to counteract them. Refiners and users of the existing fat-soluble antioxidants, whether natural or synthetic, cannot take advantage of the added protection which their immediate addition would afford, since the synthetics are only used in specific food applications, and the naturals may have flavor or other effects which are not universally acceptable.
  • Ascorbic acid which is water-soluble and fat-insoluble, is considered to be an antioxidant in some aqueous systems, although it has also been reported to be a pro-oxidant to carotenoids in orange juice.
  • prepared meats it is widely used to preserve the color, where it acts as a reducing agent which converts nitrates and nitrites to nitrous oxide, which then reacts with heme pigments to form stable red colors.
  • It is not an antioxidant in that application. It is added as a powder and becomes dissolved in the aqueous phase of the food, or as a solution in water. It has not been used in the stabilization of essentially water-insoluble substances, such as fats, oils, carotenoids, and terpene flavorings, in which applications the art has considered it ineffective. This is in accord with the teaching of the present specification.
  • the activated ascorbic acid of this invention represents a great improvement over the prior art in the stabilization of carotenoids and especially carotenoid colors.
  • the prior art uses synthetic antioxidants, such as ethoxyguin, or encapsulation in a gelatin matrix of a carotenoid dissolved in a solvent (with subsequent removal of the solvent), to protect the carotenoid from fading.
  • This invention achieves the same results without the use of objectionable solvents, as well as protecting against failure in the encapsulation process.
  • ascorbic acid may be made into an effective antioxidant for water-insoluble substrates by forming an essentially anhydrous solution or paste in a non-ionic substance (hereafter called "activator") which has both hydrophilic and lipophilic properties, and is therefore a surface-active agent, or mixtures thereof, by predisolving the ascorbic acid in a solubilizing medium, such as methanol-water, admixing this with the activator, and removing the solvent to form an essentially anhydrous composition of the activator and of ascorbic acid which, for the purposes of this specification, will be called a complex.
  • activator non-ionic substance
  • propylene glycol solubilizing medium may remain since no solvent must be removed and no surface-active agent (other than the propylene glycol itself) need be employed or included.
  • ascorbic acid when incorporated into fats, oils, terpenoids, or preparations of carotenoids, is found to be more effective, on a weight for weight basis, than ascorbyl palmitate or the common synthetic antioxidants of commerce. Without this "activation,” the ascorbic acid is essentially without effect in these same substrates.
  • FIG. 1 is a graph showing the comparative fading rates of 2% weight by weight dispersions of oleoresin paprika at 65° C. wherein the abscissa shows the percent of original color at 460 nm retained by the sample and the ordinate shows the time period in hours required for 1/3 of the color to fade, thereby to provide the standard "2/3 life", there being a control and four (4) color-stabilizing compositions in the test, the dry AA, the AP, the GMO, and the GMO plus AAA curves illustrating the effectiveness of compositions of the present invention, their superiority in stabilizing oleoresin paprika against color fading being readily apparent from the graph of FIG. 1. (See Example 4).
  • FIG. 2 is a graph showing the comparative fading rates of 2% weight by weight dispersions of oleroesin paprika at 50° C. wherein the abscissa shows the percent of original color at 460 nm retained by the sample and the ordinate shows the time period in hours required for 1/3 of the color to fade, thereby to provide the standard "2/3 life", there being a control and three (3) color-stabilizing compositions in the test, the RM, the RM plus STO plus 10-1-CC, and the RM plus AAA plus 10-1-CC plus STO curves illustrating the effectiveness of compositions of the present invention, their superiority in stabilizing oleoresin paprika against color fading being readily apparent from the graph of FIG. 2. (See Example 5).
  • an activated form of ascorbic acid which is more effective at equal dose levels than existing antioxidants for the stabilization of fats and water-immiscible oils; to provide an activated form of ascorbic acid, in a non-ionic emulsifier or surfaceactive agent or in propylene glycol, which is a tasteless and odorless antioxidant when used in foods; to provide an activated form of ascorbic acid which functions as an antioxidant in the fatty phase of a food, but which provides Vitamin C activity upon ingestion; to provide an antioxidant preparation which causes no ill effect at high levels, and which cannot be overdosed; to provide an antioxidant preparation which is more cost-effective than existing synthetic alternatives; to provide an activated ascorbic acid antioxidant which can be combined with other antioxidant to achieve synergistic results; to provide an activated ascorbic acid complex which is more effective in stabilizing carotenoids when exposed to oxygen than any other previously known antioxidant or antioxidant combination; to provide a complex of ascorbic acid which may be combined with other natural and synthetic antioxidants to achieve synergism
  • the present invention then, inter alia, comprises the following, singly or in combination:
  • a method of preparing an activated ascorbic acid having increased antioxidant activity especially in fats, oils, and fatty foods comprising the step of dissolving the ascorbic acid in (A) propylene glycol or (B) a nonionic surface-active agent, in the case of (B) in the presence of a liquid medium and removing solubilizing medium, to give an activated ascorbic acid product which is essentially anhydrous;
  • an activated ascorbic acid having increased antioxidant activity especially in fats, oils, and fatty foods, comprising ascorbic acid dissolved in propylene glycol;
  • a method of preparing an activated ascorbic acid having increased antioxidant activity especially in fats, oils, and fatty foods comprising the step of dissolving ascorbic acid in propylene glycol; such an
  • acetylated mono and diglyceride esters further esterified with a dibasic organic acid taken from the class consisting of citric and lactic acids,
  • solubilizing medium comprised a solvent selected from the group consisting of methanol, ethanol, isopropanol, and water, and mixtures thereof;
  • an AAA product or method wherein the product contains less than about 5% water, and wherein the solubilizing medium comprised a solvent selected from the group consisting of methanol, ethanol, isopropanol, and water, and mixtures thereof; such
  • an activated ascorbic acid product including a natural antioxidant selected from the group consisting of a Labiatae extract, a tea extract, and a tocopherol; such
  • the natural antioxidant is a rosemary, sage, or thyme extract
  • the natural antioxidant is selected from the group consisting of a labiatae extract, a tea extract, and a tocopherol;
  • the natural antioxidant is a rosemary, sage, or thyme extract; and such activated ascorbic acid product prepared according to any such method and/or comprising also a second nonionic surface-active agent incorporated into the antioxidant composition.
  • a method of stabilizing a carotenoid, a fat or oil, a food, or a feed which comprises the step of incorporating therein such an activated ascorbic acid product.
  • an AAA product or method wherein the amount of ascorbic acid is at least 1% by weight, preferably about 2% to about 8% by weight. Additionally, such an AAA method or product comprising a weight percentage of natural antioxidant of at least about 2% by weight. Also, such
  • nonionic surface-active agent is a monoglyceride of a fatty acid or a polyglycerol ester of a fatty acid, especially glycerol monooleate or decaglycerol capric-caprylate.
  • an AAA product or method including a Labiatae extract in amount of about 4% to about 10% by weight, especially wherein the Labiatae extract is a rosemary, sage, or thyme extract, and particularly a product stabilized therewith wherein the stabilized product is oleoresin paprika.
  • a Labiatae extract in amount of about 4% to about 10% by weight, especially wherein the Labiatae extract is a rosemary, sage, or thyme extract, and particularly a product stabilized therewith wherein the stabilized product is oleoresin paprika.
  • the emulsifiers were obtained from manufacturers, and are listed by their technical rather than trade names. They did not contain antioxidants.
  • Tea extract was derived from green tea leaves, and standardized to 16% of the antioxidant activity of the HerbaloxTM.
  • Tocopherols and ascorbyl esters were food grade and obtained from a commercial manufacturer.
  • Flour salt was food grade and obtained from a manufacturer which supplies it to seasoning houses for use in making dispersions.
  • Labiatae Extract The solvent extract of a Labiatae herb, and preferably rosemary, sage, or thyme, especially rosemary.
  • the preferable form is that described in Todd U.S. Pat. No. 4,877,635, and standardized to an antioxidant strength of about twice that of BHT in soy oil, under the standard RancimatTM conditions. It is commercially available in the form of HerbaloxTM.
  • RancimatTM An instrument which measures the induction time of an oleogenous substrate, usually at 120 degrees Celsius and at 18 liters of air per hour. This is an accepted methodology for determining relative strengths of preparations of antioxidants. The effectiveness is expressed as the induction time of the sample divided by the induction time of the control, as a percent.
  • Synergism As defined in McGraw-Hill Dictionary of Scientific and Technical Terms: "An action where the total effect of two active components is greater than the sum of their individual effects.” For example, if one additive increases the 2/3 life by 10 hours, and a second by 20 hours, and the combination of the two by 50 hours, the syngeristic effect is an additional (or plus) 20 hours.
  • acetylated mono and diglyceride esters further esterified with a dibasic organic acid taken from the class consisting of citric and lactic acids,
  • RM Rosemary Extract The extract used is HerbaloxTM, which is a commercial product available from Kalsec, Inc., standardized as to antioxidant activity, and about 20% active antioxidant compounds. It should be recognized, in this connection, that the art does not yet enable one to determine the exact concentration of active antioxidants in the extract, and 20% is merely an approximation based on the degree of dilution of the deodorized rosemary extract with soy oil.
  • a solvent which may contain water and a cosolvent, such as methanol, ethanol, isopropanol, or water alone, admixing the solution with an activator, and removing the solvent and water therefrom to give an essentially water-free composition.
  • a cosolvent with water is advantageous.
  • Methanol-water is the preferred solvent, but it should be understood that the solvents enumerated are not limiting, since any mutual solvent will be advantageous based on the new art described in this specification.
  • Desolventization and drying may be effected advantageously under vacuum, and it is possible to use azeotropic mixtures to assist in water removal. However, if sufficient vacuum is available, this is not necessary.
  • a preferred form of activator is a common non-ionic emulsifier, such as already used in foods. These are described in greater detail in Example 9, and this example illustrates a preferred method of preparation of the activated ascorbic acid using three of the preferred emulsifiers.
  • Example 4 These three preparations of activated ascorbic acid are shown, in Example 4, to be more effective than BHA and ascorbyl palmitate, which are representative of the antioxidants used in the present art.
  • the soy bean oil used in this experiment had an iodine value of 130, and a peroxide value of ⁇ 2, which indicates that oxidation has not been initiated. It represents as closely as possible the quality of oil to which the activated ascorbic acid can be added at the refinery, in order to achieve the maximum possible benefits.
  • Table 2-1 compares the effectiveness of the glycerol monooleate-activated ascorbic acid preparation of Example 1 with unactivated ascorbic acid in glycerol monooleate (GMO), i.e., glycerol monooleate to which 4% ascorbic acid had been added with warming and mixing.
  • GMO glycerol monooleate
  • This table also shows the effectiveness of the synthetic antioxidants BHA (maximum permitted use level is 0.02%), ascorbyl palmitate, and of dry ascorbic acid (AA) added directly to the oil with warming.
  • the oil soluble rosemary extract, Herbalox (®), is included as a comparative oil soluble natural antioxidant.
  • the 4% solution of AAA in glycerol monooleate was also diluted with propylene glycol in a ratio of 1:1.
  • GMO and PG were also dosed directly at 2.5%, to determine if they had antioxidant activity by themselves. They did not, which is typical of the activating emulsifiers.
  • Evaluations shown in Table 2-1 were made using a Rancimat(®) at 110 degrees C., 18 liters of air per hour, which is an accepted procedure for evaluation.
  • Schall oven technique An alternative method of evaluation of the stabilizing ability of antioxidants is called the Schall oven technique. It involves placing the oils in an oven maintained at a constant temperature (in this case at 65 deg C.) and measuring the increase in peroxide value over time. A peroxide value of 70 is considered rancid.
  • Table 2-2 shows the Schall oven stabilites of oils stabilized with preparations made according to this disclosure, as well as those made with two other conventional antioxidants using the same oil and conditions.
  • the oils dosed with PG, 10-1-CC, and 8-1-0 additions of 2.5% of the AAA-activator mixtures were made, agitated, and separated. This left the supernatant soy oil saturated with the activated ascorbic acid, which simplifies dosing on a commercial scale. Of course, dosing below saturation levels is also effective.
  • this example shows that ascorbic acid added directly to soy oil, or when added directly to a non-ionic activator, is not effective as an antioxidant in vegetable oil. It also shows that when activated, ascorbic acid is more powerful in retarding rancidity than other fat soluble antioxidants at equal dose levels.
  • a 6.67% solution of AAA in propylene glycol was prepared by mixing 6.67 g of ascorbic acid with 93.3 g of propylene glycol and warming. 30 g of this was mixed with 70 g of glycerol monooleate. This mixture was added to soy oil and to canola oil at the levels shown in Table 3-1. Clarity is noted, as well as the induction time at 110 deg C. on the Rancimat(®). Ascorbic acid and BHA were also added directly to Canola Oil at 0.02 and 0.04% respectively. Canola oil is very high in omega-3 unsaturated fatty acids, which are also present in fish oil, and which are considered beneficial to health. It is clear that the activated ascorbic acid functions with omega-3 fatty acids as well as with the more common unsaturated fatty acids present in such oils as soy, sunflower, sesame, and safflower.
  • AAA has great effectiveness in soy oil, but that it has a totally unanticipated positive effect on canola oil, whereas neither BHA nor unactivated ascorbic have any effect.
  • the behavior in high omega-3 fish oils is similar.
  • the activated ascorbic acid preparations are also surprisingly effective in the stabilization of paprika pigments, whereas unactivated ascorbic acid was not.
  • a control was made by diluting the 120,000 color value extract with an equal part of soy oil.
  • a second control was made using 50 parts of oleoresin, 49 parts of soy oil, and one part of ascorbic acid added directly to the mixture with agitation and warming.
  • a third set of controls was made using fifty part of oleoresin, 26 parts of soy oil, and 24 parts of the emulsifiers.
  • a comparative control incorporated, with warming, ascorbyl palmitate at 0.6% into the mixture of equal parts of oleoresin and soy oil, and BHA at 0.2%, ten times its permitted level.
  • This oleoresin was plated onto flour salt at a concentration of 2%, and this dispersion was weighed into test tubes (2 g portions) which in turn were placed in an oven at 65 deg C. The tubes were periodically withdrawn, and the color value of the dispersion evaluated by extraction with acetone and reading the absorbance in a spectrophotometer. The time it took for 1/3 of the color to fade is designated the 2/3 life of the preparation, and indicates the relative stability.
  • Table 4-1 shows the remarkable effect of the activated ascorbic acid on the stability of the paprika color.
  • FIG. 1 shows the actual plots of % of original color vs time for the control, AA, AP, GMO, and GMO+AAA of Table 4-1. It will be noted that there are essentially three sets of curves: the control and unactivated AA, the AP and GMO, and the GMO+activated ascorbic acid. The dramatic effect of activated ascorbic acid is obvious, as is the inactivity of ascorbic acid per se.
  • Table 4-1 also shows that the emulsifier-activators used in this example have a positive effect on the stability of the paprika, even though they are slightly prooxidant on the Rancimat(®) test. Because of this activity, the use of these emulsifiers for the paprika and other carotenoid stabilization systems is particularly advantageous. The usefulness of the emulsifiers in assisting in the stabilization of paprika is further described in a copending application.
  • compositions of the oleoresins which were evaluated is provided in Table 5-1, which also reports the increase in 2/3 lives at 65 deg. C. due to the additives.
  • the synergism is also shown, which is expressed as the difference between the actual increase of the sample and the added increase of the two components by themselves. This increase is also expressed as a % of the 2/3 life of the control, which was 36 hours.
  • the synergistic effect is increased by the addition of sorbitan trioleate (STO), and lowering the temperature of the oven to 50 degrees C., as shown in the following example and portrayed in FIG. 2.
  • STO sorbitan trioleate
  • the ascorbic acid was activated in 10-1-CC by the method of Example 1, using methanol-water and removing it to less than 1% water content.
  • Ethoxyquin a synthetic antioxidant of questionable safety, is explicitly allowed for the stabilization of pigments in paprika for use in human food, at a level of no more than 0.01%, it being the most powerful carotenoid stabilizer heretofore known. It is also permitted for use in animal feeds to stabilize carotenoids. Its effectiveness at a dose of 0.01% is on the same order of magnitude as rosemary extract at 2%.
  • the activated ascorbic acid of this invention obviously provides an improved, healthy, and economical alternative for stabilizing paprika, food, and animal feeds.
  • activated ascorbic acid is not limited to oleoresin paprika, but is also shown with other carotenoids, such as bixin and norbixin, natural carotenes and xanthophylls, and synthetic carotenoids such as beta-carotene, beta-apo-8-carotenal, canthaxanthin, and the like.
  • carotenoids such as bixin and norbixin, natural carotenes and xanthophylls, and synthetic carotenoids such as beta-carotene, beta-apo-8-carotenal, canthaxanthin, and the like.
  • Bixin Fifty parts of a commercial pop-corn color, Vegetone®, containing 5.3% bixin and 1.8% curcumin (a non-carotenoid pigment), was used as is; with 3.5 parts added BHT; with 4 parts added Herbalox-O®; and with 4 parts added Herbalox-O® plus 25 parts of 4% activated ascorbic acid in 10-1-CC and in GMO. Each preparation was diluted to a total of 100 parts with soy bean oil, to give preparations of equal pigment content.
  • the table shows that, of the two activating emulsifiers, glycerol monooleate is preferable to decaglycerol mono capric-caprylate.
  • Beta-carotene 13 parts of a 30% suspension of beta-carotene was mixed with 62 parts of soy bean oil, to give a liquid suspension (Solution A). This in turn was added to soy oil in an amount to give 0.0175% beta carotene in the oil. This was the control solution. 25 parts of 4% activated ascorbic acid in glycerol monooleate was added to 75 parts of Solution A, to make Solution B. This in turn was added to soy oil to give a 0.0175% concentration of beta-carotene, which was the test solution. Both oils were immersed in an oil bath at 144 deg C. for 10 minutes.
  • Animal fats are considered to be less stable than vegetable oils.
  • Poultry fat in particular is very unstable, due to its high degree of unsaturation.
  • This example demonstrates the efficacy of activated ascorbic acid in stabilizing chicken fat. It is equally useful for stabilizing pork fat, high omega-3 fish oils (see Example 3 and the related canola oil), and more stable beef fat.
  • Freshly rendered chicken fat was clarified, and dosed as shown in Example 7-1 with the activated ascorbic acid which was activated as indicated.
  • the fats were tested for induction times in hours on the Rancimat at 110 degrees C., and results as well as ratios to controls, are reported.
  • the Schall oven stabilities at 65 deg. C. were also determined, with the peroxide values at the end of 4 and 7 days being reported.
  • the activated ascorbic acid can also be used to stabilize paprika.
  • paprika flesh was dried to 4% moisture and ground.
  • 2.5% of a 4% solution of AAA in GMO was added with agitation.
  • sufficient water was added to rehydrate to the normal level of 8-12%, and the AAA in GMO added.
  • Stability was evaluated at 65 deg. C., and the 2/3 life of both samples was 158% of the control. This example not only shows that AAA protects carotenoids embedded in paprika flesh, but that normal rehydration which is done artificially by adding water, or naturally by allowing the flesh to stand in air, does not interfere.
  • Such a stabilized paprika pigment should be used in animal feeds, such as poultry or fish, wherein the carotenoids are used to color the yolk or flesh of the animals.
  • the invention is equally effective in stabilizing marigold pigments, or synthetic carotenoids such as canthaxanthin, when used in feeds.
  • marigold pigments or synthetic carotenoids such as canthaxanthin, when used in feeds.
  • the synergistic combination of the AAA with other natural antioxidants, and non-ionic surface active agents, is of course beneficial.
  • AAA retards the degradation of carotenoids when exposed to heat. Since it also retards oxidation of fats when heated, it is particularly effective in deep fat frying operations, wherein it is desired to prevent color loss as well as initiation of fat oxidation. It is equally well adapted to the stabilization of fat, or of pigmented fat in a batter, prior to baking. Synergistic combinations with other natural antioxidants are beneficial in these applications, to further increase the shelf life of the snack or baked food, and preserve the brightness of the color.
  • antioxidants are used in dressings, where the oil is added on top of the vinegar.
  • the AAA if added to the oil at the refinery, will prevent initiation of oxidation prior to manufacture of the mayonaise, and thereby increase its shelf life.
  • AAA is preferably added to vegetable oil or animal fat at the refinery, to inhibit initiation of oxidation.
  • the AAA inhibits degradation of omega three fatty acids, which are an important constituent of fish oils. Addition of the AAA to fish oils immediately at the end of refining is also advantageous. These fish oils then have increased stability when incorporated into capsules.
  • preparations of Vitamin A, as well as retinoids, which are related to carotenoids can be stabilized. Cloudiness of the oil is not objectionable in these applications, so that overdosing as may occur in practise is not harmful.
  • the AAA is also useful for the stabilization of terpenes and flavorings, such as limonene, orange oil or spice extracts. It is also an effective antioxidant in a chewing gum base, and such a stabilized base will enhance the stability of the gum flavoring, such as a mint oil.
  • terpenes and flavorings such as limonene, orange oil or spice extracts.
  • limonene, orange oil or spice extracts such as limonene, orange oil or spice extracts.
  • a stabilized base will enhance the stability of the gum flavoring, such as a mint oil.
  • non-ionic emulsifiers are separated into five classes: (1) those exhibiting strong stabilizing and synergistic properties; (2) those exhibiting strong activating properties; (3) those with modest activating properties and modest synergistic properties; (4) propylene glycol; and (5) those with strongly destabilizing effect and/or inability to activate the ascorbic acid.
  • the latter class is specifically excluded from the field of this invention, since it has a strong negative effect on the synergism which is expressed between AAA and rosemary, tocopherols, and the like, as well as on the stability of the dispersions of the oils and/or pigments on solid substrates.
  • this invention enables the practitioner to design a stabilizing system for paprika pigments, other carotenoids, and fats and oils which is best adapted to the physical needs of the specific food in which the coloring or oil will be used.
  • sorbitan esters such as mono and tri oleates and stearates
  • polyglycerol esters such as octaglycerol monooleate, decaglycerol capric-caprylate, and decaglycerol tetraoleate
  • mono-diglycerides such as glycerol mono-oleate
  • citric acid esters of mono-diglycerides citric acid esters of mono-diglycerides
  • polyoxyethylene derivatives such as polyoxyethylene
  • Emulsifiers in the second class are the preferred embodiment of this invention, whereas those in the third and fourth classes are less preferred, and those in the fifth class are surprisingly deleterious.
  • Those in the first class are preferred in combination with those of the second class, for expression of synergism with natural antioxidants. It is remarkable that, except for the polyoxyethylene derivatives, there is no structural relationship between the emulsifiers and the classes into which they fall.
  • Emulsifiers falling within the first four classes are within the scope of this invention, and the practitioner should recognize that even though it may appear desirable to include an emulsifier of the fifth class in a composition, because of its superior emulsification properties, it will detract from the stabilizing emulsifiers and synergisms, and every effort to avoid inclusion of even incidental amounts should be made.
  • the AAA preparation remains effective in emulsions, in which it is incorporated into the oil phase.
  • mayonnaise which is a water in oil emulsion
  • This oil phase is subjected to oxidation due to entrained air, and is protected by the AAA.
  • unactivated ascorbic acid is added directly, it dissolves in the aqueous internal phase of the emulsion, and is without effect in the oil.
  • the soy bean oil used in this example has been refined so as to remove all lecithin from the crude oil.
  • the presence of lecithin causes discoloration and flavor degradation of the oil on storage, and is therefor removed from refined vegetable oils.
  • the prior art shows a ternary mixture of tocopherols, lecithin, (an ionic phospholipid), and ascorbic acid as an effective antioxidant in such oils. Perhaps the degradation of the oil due to lecithin is inhibited by the tocopherol-ascorbic acid combination, thereby taking advantage of the strong anti-oxidant power of lecithin as measured by the Rancimat and peroxide values.
  • This example uses soy oil to which has been added GMO/AAA, GMO/AA, lecithin, lecithin+dry AA, and lecithin+AA dissolved in solvent and then desolventized.
  • the GMO contained 4% AA or AAA and was added at a 2.5% level.
  • the lecithin contained 10% AA or dissolved AA.
  • the level of AA or AAA in the soy oil was 0.1%.
  • the Rancimat stabilities at 110 deg. were observed, as was discoloration after storage at ambient for three months.
  • the AAA of this invention created in a non-ionic emulsifier which is a fatty acid ester of a polyol or polybasic organic acid, or propylene glycol, is different in performance and reactivity than similarly prepared combinations of AA and lecithin. While the latter is not acceptable per se for incorporation in fats and oils and the stabilization of carotenoids, the products of this invention are highly advantageous, neither being pro-oxidant or discolorants as dosage levels increase.
  • the activation of AA in the non-ionic emulsifiers changes the AA from a prooxidant to an AAA form which is strongly antioxidant; whereas the predissolution of AA and lecithin weakens the antioxidant power over dry AA+lecithin, while accelerating the discoloration.
  • preferred nonionic surface-active agents are monoglycerides of a fatty acid and polyglycerol esters of a fatty acid, especially glycerolmonooleate and decaglycerol capric-caprylate and, where two nonionic surface-active agents are present, they are preferably selected from among these groups.
  • vegetable oil especially soybean oil
  • carotenoids especially oleoresin paprika
  • ascorbic acid is preferably present in amount of at least about 1% by weight, preferably about 2% to 8% by weight of the total composition and, when present, the natural antioxidant is preferably present in a minimum amount of 2% of the activated ascorbic acid preparation, preferably 4% to 10% by weight or even higher, and the same percentages prevail for Labiatae extracts, such as rosemary, sage, or thyme extract, tea extract, and tocopherols, the only upper limit being one of economics and the only lower limit being one of operativeness.
  • the resulting product is in each case a solution of the activated ascorbic acid in the propylene glycol or nonionic surface-active agent, the exact definition of the product as a solution or a solution-suspension being fundamentally dependent upon the amount of the ascorbic acid introduced into the composition, the more introduced the more likely that the product will be a solution-suspension rather than a simple solution.
  • the present invention provides an activated ascorbic acid and compositions thereof, especially such essentially anhydrous compositions as embody propylene glycol or a nonionic surface-active agent, such products having increased antioxidant activity in fats, oils, carotenoids, and fatty foods, especially such materials and products as are exposed to oxidative stress, as well as a method of stabilizing such materials and products against oxidative discoloration, feeds and foodstuffs which may encounter oxidative stress stabilized with a composition of the invention, and a method of stabilizing a feed or foodstuff or flavoring with such a more effective antioxidant composition of the invention.
  • the stabilization of carotenoid pigments may advantageously be carried out in the presence of a particulate edible solid substrate for the carotenoid pigment.
  • Synergistic effects are obtained by the incorporation of a natural antioxidant in such compositions and methods and the antioxidant effectiveness of the compositions and methods is further greatly enhanced by inclusion of a natural Labiatae antioxidant, tea extract, or a tocopherol therein, and antioxidant power and stabilization effectiveness is frequently further improved by inclusion therein of a second nonionic surface-active agent. All of the foregoing provide long-awaited solutions to previously-existing oxidation and instability problems not adequately solved by the prior art.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Food Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Nutrition Science (AREA)
  • Microbiology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Emergency Medicine (AREA)
  • Inorganic Chemistry (AREA)
  • Botany (AREA)
  • Animal Husbandry (AREA)
  • Zoology (AREA)
  • Food Preservation Except Freezing, Refrigeration, And Drying (AREA)
  • Fats And Perfumes (AREA)
  • Anti-Oxidant Or Stabilizer Compositions (AREA)
  • Coloring Foods And Improving Nutritive Qualities (AREA)
  • Edible Oils And Fats (AREA)
US07/544,248 1990-06-26 1990-06-26 Activated ascorbic acid antioxidant compositions and carotenoids, fats, and foods stabilized therewith Expired - Lifetime US5084293A (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
US07/544,248 US5084293A (en) 1990-06-26 1990-06-26 Activated ascorbic acid antioxidant compositions and carotenoids, fats, and foods stabilized therewith
JP3511949A JPH05509115A (ja) 1990-06-26 1991-06-24 活性アスコルビン酸抗酸化剤組成物およびこれにより安定化されたカロチノイド、脂肪および食品
PCT/US1991/004503 WO1992000019A1 (en) 1990-06-26 1991-06-24 Activated ascorbic acid antioxidant compositions and carotenoids, fats, and foods stabilized therewith
EP91912368A EP0536257B1 (de) 1990-06-26 1991-06-24 Aktivierte ascorbinsäure antioxidationzusammensetzungen und damit stabilisierte carotinoiden, fette und nahrungsmittel
AT91912368T ATE122855T1 (de) 1990-06-26 1991-06-24 Aktivierte ascorbinsäure antioxidationzusammensetzungen und damit stabilisierte carotinoiden, fette und nahrungsmittel.
DE69110045T DE69110045T2 (de) 1990-06-26 1991-06-24 Aktivierte ascorbinsäure antioxidationzusammensetzungen und damit stabilisierte carotinoiden, fette und nahrungsmittel.
CA002045416A CA2045416A1 (en) 1990-06-26 1991-06-25 Activated ascorbic acid antioxidant compositions and carotenoids, fats, and foods stabilized therewith
IE220591A IE912205A1 (en) 1990-06-26 1991-06-25 Activated ascorbic acid antioxidant compositions and carotenoids, fats, and foods stabilized therewith

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US07/544,248 US5084293A (en) 1990-06-26 1990-06-26 Activated ascorbic acid antioxidant compositions and carotenoids, fats, and foods stabilized therewith

Publications (1)

Publication Number Publication Date
US5084293A true US5084293A (en) 1992-01-28

Family

ID=24171394

Family Applications (1)

Application Number Title Priority Date Filing Date
US07/544,248 Expired - Lifetime US5084293A (en) 1990-06-26 1990-06-26 Activated ascorbic acid antioxidant compositions and carotenoids, fats, and foods stabilized therewith

Country Status (8)

Country Link
US (1) US5084293A (de)
EP (1) EP0536257B1 (de)
JP (1) JPH05509115A (de)
AT (1) ATE122855T1 (de)
CA (1) CA2045416A1 (de)
DE (1) DE69110045T2 (de)
IE (1) IE912205A1 (de)
WO (1) WO1992000019A1 (de)

Cited By (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5230916A (en) * 1991-01-07 1993-07-27 Kabi Pharmacia Ab Ascorbic acid complex having antioxidant function and improved solubility in lipid materials
US5230836A (en) * 1991-06-20 1993-07-27 Kalamazoo Holdings, Inc. Low micron-sized ascorbic acid particles, especially a suspension thereof in a medium in which they are insoluble, and the use thereof as an antioxidant for mediums in which the particles remain insoluble
US5234702A (en) * 1992-03-19 1993-08-10 Abbott Laboratories Antioxidant system for powdered nutritional products
WO1996039869A1 (en) * 1995-06-07 1996-12-19 Mars, Incorporated Health food product
US5869116A (en) * 1997-01-06 1999-02-09 Yoo; Byong W. Method for preparing kimchi
US5948388A (en) * 1998-06-12 1999-09-07 Soft Gel Technologies, Inc. Chewable softgel oral hygiene product
US5976584A (en) * 1997-11-07 1999-11-02 Yoo; Byong W. Method for preparing kimchi
US6013304A (en) * 1996-12-13 2000-01-11 Kalamazoo Holdings, Inc. High temperature countercurrent solvent extraction of herb or spice solids
US6210701B1 (en) * 1999-04-30 2001-04-03 Healthcomm International, Inc. Medical food for treating inflammation-related diseases
US6524637B2 (en) * 1998-03-20 2003-02-25 Danisco A/S Composition providing a stable suspension of a particulate component
US20040091553A1 (en) * 2002-11-12 2004-05-13 West Agro, Inc Composition and method for mammary disinfection during winter conditions
US20050019373A1 (en) * 2003-07-24 2005-01-27 Materials Evolution And Development Usa, Inc. Nucleic acid antioxidant compositions, methods for obtaining such compositions and formulations thereof
US6858247B2 (en) * 1999-06-16 2005-02-22 Kao Corporation Fat composition
WO2005019397A1 (en) * 2003-08-22 2005-03-03 Oy Vegaoils Ltd Antioxidant and its use
EP1558214A1 (de) * 2002-11-08 2005-08-03 Hanmi Pharm. Co., Ltd. Mikroemulsionskonzentrate für die oraleverabreichung von wasserunlöslichem arzneimittel gegen erkältungen und herstellungsverfahren dafür
EP1726632A1 (de) * 2004-03-19 2006-11-29 Mitsubishi Chemical Corporation Abbauinhibitor
US20070042184A1 (en) * 2003-08-22 2007-02-22 Danisco A/S Microcapsules
US20070065547A1 (en) * 2003-08-22 2007-03-22 Danisco A/S Encapsulated antimicrobial material
US20070104765A1 (en) * 2005-11-09 2007-05-10 Faltys Gary L Livestock and poultry feed additive composition
US20070199342A1 (en) * 2004-01-02 2007-08-30 Young Hee Kang Method of manufacturing ketchup in red, green or yellow color using liquid kimchi
WO2008127086A1 (en) * 2007-04-12 2008-10-23 Malaysian Palm Oil Board Palm phenolics and flavonoids as potent biological and chemical antioxidants for applications in foods and edible oils.
US7910149B2 (en) 2001-11-05 2011-03-22 Danisco A/S Liquid bread improver, the use and the process for producing thereof
US20120183654A1 (en) * 2011-01-18 2012-07-19 Kemin Industries, Inc. Method of Stabilization of Pet Food Palatant and Fat Systems
KR20190079835A (ko) * 2017-12-28 2019-07-08 김주호 일광 및 고온조건에 안정한 l-아스코르빈산을 함유하는 화장료 조성물
USD862031S1 (en) 2008-06-27 2019-10-08 Mars, Incorporated Food product
US20200205428A1 (en) * 2017-09-12 2020-07-02 Purac Biochem B.V. Meat treatment
US10835566B2 (en) 2013-05-14 2020-11-17 Mars, Incorporated Joint care composition
CN113383818A (zh) * 2021-06-11 2021-09-14 江南大学 一种提高夏威夷果中抗氧化剂渗透效率的方法
CN115486530A (zh) * 2022-10-21 2022-12-20 湖南祥民制药有限公司 一种迷迭香的冷冻干燥方法

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0692934A4 (de) * 1993-04-01 1997-11-26 Kalamazoo Holdings Inc Fettlösliche antioxidant lösungen mit catechin aus grünem tee
GB9323588D0 (en) 1993-11-16 1994-01-05 Cortecs Ltd Hydrophobic preparation
GB9424908D0 (en) * 1994-12-09 1995-02-08 Cortecs Ltd Anti-Oxidant Compositions
AU5416998A (en) * 1997-10-14 1999-05-03 Quest International B.V. Preparation for the enhancement of the antioxidant status of cells
FR2772042A1 (fr) * 1997-12-10 1999-06-11 Union Des Fabricants D Aliment Composition anti-oxydante, son procede de preparation et ses utilisations
WO2001096506A1 (fr) * 2000-06-12 2001-12-20 Fuji Oil Company, Limited Procede servant a produire de la graisse
DE10158447B4 (de) * 2001-11-30 2005-02-10 Aquanova German Solubilisate Technologies (Agt) Gmbh Ascorbinsäure-Solubilisat

Citations (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2511804A (en) * 1950-06-13 Antioxidant salt
US3008832A (en) * 1959-09-24 1961-11-14 Heller & Company B Stabilized seasoning composition and method of making the same
US3110598A (en) * 1959-09-08 1963-11-12 Hoffmann La Roche Process of making a carotenoid preparation
US3316101A (en) * 1965-08-03 1967-04-25 Hoffmann La Roche Stabilizing carotenoid compositions
US3455838A (en) * 1966-04-22 1969-07-15 Nat Starch Chem Corp Method of encapsulating water-insoluble substances and product thereof
US3767825A (en) * 1971-06-18 1973-10-23 Merck & Co Inc Method of coating food particles with a blend of vitamins a and c
US3800047A (en) * 1971-10-21 1974-03-26 American Potato Co Process for producing dehydrated potato products fortified with stable vitamin c
US3833743A (en) * 1970-03-17 1974-09-03 Merck & Co Inc Solubilization of water and aqueous solutions in non-aqueous liquids
US3899598A (en) * 1974-02-15 1975-08-12 Gen Foods Corp Fortified gelating dessert powder and process
US3906116A (en) * 1972-09-25 1975-09-16 Bush Boake Allen Ltd Concentrated oleoresin products and emulsification process for preparing them
US3966632A (en) * 1974-06-06 1976-06-29 G. D. Searle & Co. Vegetable oil emulsion
US4070488A (en) * 1975-11-25 1978-01-24 Davis Rachel D Nutritive composition
US4187322A (en) * 1975-11-30 1980-02-05 Hoffmann-La Roche Inc. Powder compositions containing vitamin C active component
US4187332A (en) 1978-10-19 1980-02-05 M. Lowenstein & Sons, Inc. Process for producing light-reflective fabrics
US4451488A (en) * 1981-06-22 1984-05-29 The Quaker Oats Company Food bar
US4504499A (en) * 1983-04-25 1985-03-12 Basf Wyandotte Corporation Heat-stabilized, carotenoid-colored edible oils
US4614656A (en) * 1984-05-14 1986-09-30 Lever Brothers Company Two phase margarine
US4877635A (en) * 1985-12-20 1989-10-31 Kalamazoo Holdings, Inc. Herb flavoring and/or antioxidant composition and process
US4925681A (en) * 1983-12-15 1990-05-15 Nestec S.A. Process for inhibiting lipid oxidation in food and composition thereby
EP0326829B1 (de) * 1988-02-03 1994-04-27 Societe Des Produits Nestle S.A. Synergetische Antioxydationsmischung

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2500543A (en) 1945-07-20 1950-03-14 Griffith Laboratories Antioxidant
GB761010A (en) * 1953-08-06 1956-11-07 Eastman Kodak Co Antioxidant concentrates
JPS61127786A (ja) 1984-11-27 1986-06-16 Nippon Oil & Fats Co Ltd 油脂可溶化物

Patent Citations (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2511804A (en) * 1950-06-13 Antioxidant salt
US3110598A (en) * 1959-09-08 1963-11-12 Hoffmann La Roche Process of making a carotenoid preparation
US3008832A (en) * 1959-09-24 1961-11-14 Heller & Company B Stabilized seasoning composition and method of making the same
US3316101A (en) * 1965-08-03 1967-04-25 Hoffmann La Roche Stabilizing carotenoid compositions
US3455838A (en) * 1966-04-22 1969-07-15 Nat Starch Chem Corp Method of encapsulating water-insoluble substances and product thereof
US3833743A (en) * 1970-03-17 1974-09-03 Merck & Co Inc Solubilization of water and aqueous solutions in non-aqueous liquids
US3767825A (en) * 1971-06-18 1973-10-23 Merck & Co Inc Method of coating food particles with a blend of vitamins a and c
US3800047A (en) * 1971-10-21 1974-03-26 American Potato Co Process for producing dehydrated potato products fortified with stable vitamin c
US3906116A (en) * 1972-09-25 1975-09-16 Bush Boake Allen Ltd Concentrated oleoresin products and emulsification process for preparing them
US3899598A (en) * 1974-02-15 1975-08-12 Gen Foods Corp Fortified gelating dessert powder and process
US3966632A (en) * 1974-06-06 1976-06-29 G. D. Searle & Co. Vegetable oil emulsion
US4070488A (en) * 1975-11-25 1978-01-24 Davis Rachel D Nutritive composition
US4187322A (en) * 1975-11-30 1980-02-05 Hoffmann-La Roche Inc. Powder compositions containing vitamin C active component
US4187332A (en) 1978-10-19 1980-02-05 M. Lowenstein & Sons, Inc. Process for producing light-reflective fabrics
US4451488A (en) * 1981-06-22 1984-05-29 The Quaker Oats Company Food bar
US4504499A (en) * 1983-04-25 1985-03-12 Basf Wyandotte Corporation Heat-stabilized, carotenoid-colored edible oils
US4925681A (en) * 1983-12-15 1990-05-15 Nestec S.A. Process for inhibiting lipid oxidation in food and composition thereby
US4614656A (en) * 1984-05-14 1986-09-30 Lever Brothers Company Two phase margarine
US4877635A (en) * 1985-12-20 1989-10-31 Kalamazoo Holdings, Inc. Herb flavoring and/or antioxidant composition and process
EP0326829B1 (de) * 1988-02-03 1994-04-27 Societe Des Produits Nestle S.A. Synergetische Antioxydationsmischung

Cited By (51)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5230916A (en) * 1991-01-07 1993-07-27 Kabi Pharmacia Ab Ascorbic acid complex having antioxidant function and improved solubility in lipid materials
US5230836A (en) * 1991-06-20 1993-07-27 Kalamazoo Holdings, Inc. Low micron-sized ascorbic acid particles, especially a suspension thereof in a medium in which they are insoluble, and the use thereof as an antioxidant for mediums in which the particles remain insoluble
US5296249A (en) * 1991-06-20 1994-03-22 Kalamazoo Holdings Company, Inc. Low micron-sized ascorbic acid particles, especially a suspension thereof in a medium in which they are insoluble, and the use thereof as an antioxidant for mediums in which the particles remain insoluble
US5234702A (en) * 1992-03-19 1993-08-10 Abbott Laboratories Antioxidant system for powdered nutritional products
US5834044A (en) * 1995-06-07 1998-11-10 Mars, Incorporated Method of making a health food product containing anti-oxidants
US5643623A (en) * 1995-06-07 1997-07-01 Mars Incorporated Health food product and its uses
WO1996039869A1 (en) * 1995-06-07 1996-12-19 Mars, Incorporated Health food product
US6013304A (en) * 1996-12-13 2000-01-11 Kalamazoo Holdings, Inc. High temperature countercurrent solvent extraction of herb or spice solids
US6074687A (en) * 1996-12-13 2000-06-13 Kalamazoo Holdings, Inc. High temperature countercurrent solvent extraction of capsicum solids
US5869116A (en) * 1997-01-06 1999-02-09 Yoo; Byong W. Method for preparing kimchi
US5976584A (en) * 1997-11-07 1999-11-02 Yoo; Byong W. Method for preparing kimchi
US6524637B2 (en) * 1998-03-20 2003-02-25 Danisco A/S Composition providing a stable suspension of a particulate component
US5948388A (en) * 1998-06-12 1999-09-07 Soft Gel Technologies, Inc. Chewable softgel oral hygiene product
US6210701B1 (en) * 1999-04-30 2001-04-03 Healthcomm International, Inc. Medical food for treating inflammation-related diseases
US6858247B2 (en) * 1999-06-16 2005-02-22 Kao Corporation Fat composition
US20110135790A1 (en) * 2001-11-05 2011-06-09 Erik Jensen Liquid Bread Improver, The Use And The Process For Producing Thereof
US7910149B2 (en) 2001-11-05 2011-03-22 Danisco A/S Liquid bread improver, the use and the process for producing thereof
EP1558214A1 (de) * 2002-11-08 2005-08-03 Hanmi Pharm. Co., Ltd. Mikroemulsionskonzentrate für die oraleverabreichung von wasserunlöslichem arzneimittel gegen erkältungen und herstellungsverfahren dafür
EP1558214A4 (de) * 2002-11-08 2009-12-09 Hanmi Pharm Ind Co Ltd Mikroemulsionskonzentrate für die oraleverabreichung von wasserunlöslichem arzneimittel gegen erkältungen und herstellungsverfahren dafür
US20040091553A1 (en) * 2002-11-12 2004-05-13 West Agro, Inc Composition and method for mammary disinfection during winter conditions
US20050019373A1 (en) * 2003-07-24 2005-01-27 Materials Evolution And Development Usa, Inc. Nucleic acid antioxidant compositions, methods for obtaining such compositions and formulations thereof
US7125859B2 (en) 2003-07-24 2006-10-24 Materials Evolution And Development Usa, Inc. Nucleic acid antioxidant compositions, methods for obtaining such compositions and formulations thereof
US7605141B2 (en) 2003-07-24 2009-10-20 Materials Evolution And Development Usa, Inc. Nucleic acid antioxidant compositions, methods for obtaining such compositions and formulations thereof
US20070112064A1 (en) * 2003-07-24 2007-05-17 Lyles Mark B Nucleic acid antioxidant compositions, methods for obtaining such compositions and formulations thereof
US20070104809A1 (en) * 2003-08-22 2007-05-10 Danisco A/S Composition comprising a bacteriocin and an extract from a plant of the labiatae family
WO2005019397A1 (en) * 2003-08-22 2005-03-03 Oy Vegaoils Ltd Antioxidant and its use
US10271557B2 (en) 2003-08-22 2019-04-30 Dupont Nutrition Biosciences Aps Composition comprising a bacteriocin and an extract from a plant of the Labiatae family
US20070231438A1 (en) * 2003-08-22 2007-10-04 Oy Vegaoils Ltd. Antioxidant and Its Use
US8337923B2 (en) 2003-08-22 2012-12-25 Dupont Nutrition Biosciences Aps Encapsulated antimicrobial material
US20070042184A1 (en) * 2003-08-22 2007-02-22 Danisco A/S Microcapsules
US20070065547A1 (en) * 2003-08-22 2007-03-22 Danisco A/S Encapsulated antimicrobial material
US20070199342A1 (en) * 2004-01-02 2007-08-30 Young Hee Kang Method of manufacturing ketchup in red, green or yellow color using liquid kimchi
EP2261304A3 (de) * 2004-03-19 2011-04-20 Mitsubishi Chemical Corporation Abbauinhibitor
AU2005223551B2 (en) * 2004-03-19 2010-07-01 Mitsubishi Chemical Corporation Anti-degradation agent
US20080044540A1 (en) * 2004-03-19 2008-02-21 Hirotsugu Kido Anti-Degradation Agent
EP1726632A1 (de) * 2004-03-19 2006-11-29 Mitsubishi Chemical Corporation Abbauinhibitor
US20110178173A1 (en) * 2004-03-19 2011-07-21 Mitsubishi Chemical Corporation Anti-degradation agent
EP1726632A4 (de) * 2004-03-19 2008-04-16 Mitsubishi Chem Corp Abbauinhibitor
US20070104765A1 (en) * 2005-11-09 2007-05-10 Faltys Gary L Livestock and poultry feed additive composition
WO2008127086A1 (en) * 2007-04-12 2008-10-23 Malaysian Palm Oil Board Palm phenolics and flavonoids as potent biological and chemical antioxidants for applications in foods and edible oils.
US20100183786A1 (en) * 2007-04-12 2010-07-22 Yew Ai Tan Palm phenolics and flavonoids as potent biological and chemical antioxidants for applications in foods and edible oils
USD862031S1 (en) 2008-06-27 2019-10-08 Mars, Incorporated Food product
US20120183654A1 (en) * 2011-01-18 2012-07-19 Kemin Industries, Inc. Method of Stabilization of Pet Food Palatant and Fat Systems
US10835566B2 (en) 2013-05-14 2020-11-17 Mars, Incorporated Joint care composition
US20200205428A1 (en) * 2017-09-12 2020-07-02 Purac Biochem B.V. Meat treatment
US20240099319A1 (en) * 2017-09-12 2024-03-28 Purac Biochem B.V. Meat treatment
KR20190079835A (ko) * 2017-12-28 2019-07-08 김주호 일광 및 고온조건에 안정한 l-아스코르빈산을 함유하는 화장료 조성물
CN113383818A (zh) * 2021-06-11 2021-09-14 江南大学 一种提高夏威夷果中抗氧化剂渗透效率的方法
CN113383818B (zh) * 2021-06-11 2022-09-06 江南大学 一种提高夏威夷果中抗氧化剂渗透效率的方法
CN115486530A (zh) * 2022-10-21 2022-12-20 湖南祥民制药有限公司 一种迷迭香的冷冻干燥方法
CN115486530B (zh) * 2022-10-21 2024-03-26 湖南祥民制药有限公司 一种迷迭香的冷冻干燥方法

Also Published As

Publication number Publication date
CA2045416A1 (en) 1991-12-27
DE69110045D1 (de) 1995-06-29
JPH05509115A (ja) 1993-12-16
IE912205A1 (en) 1992-01-01
EP0536257B1 (de) 1995-05-24
WO1992000019A1 (en) 1992-01-09
DE69110045T2 (de) 1995-10-05
ATE122855T1 (de) 1995-06-15
EP0536257A1 (de) 1993-04-14

Similar Documents

Publication Publication Date Title
US5084293A (en) Activated ascorbic acid antioxidant compositions and carotenoids, fats, and foods stabilized therewith
US5290481A (en) Low micron-sized ascorbic acid particles, especially a suspension thereof in a medium in which they are insoluble, and the use thereof as an antioxidant for mediums in which the particles remain insoluble
US5079016A (en) Color-stabilized carotenoid pigment compositions and foods colored therewith having increased resistance to oxidative color fading
US5527552A (en) Lipid-soluble green tea catechin antioxidant solutions
de Abreu et al. Lipid damage during frozen storage of Atlantic halibut (Hippoglossus hippoglossus) in active packaging film containing antioxidants
US5077069A (en) Composition of natural antioxidants for the stabilization of polyunsaturated oils
De Abreu et al. Evaluation of the effectiveness of a new active packaging film containing natural antioxidants (from barley husks) that retard lipid damage in frozen Atlantic salmon (Salmo salar L.)
JP3113319B2 (ja) 天然抗酸化剤組成物
US5059437A (en) Color-stabilized paprika pigment compositions and foods colored therewith having increased resistance to oxidative color fading
WO1994022322A1 (en) Solid microcrystalline green tea catechin antioxidants for lipids
Tanislav et al. The oxidative quality of bi-, oleo-and emulgels and their bioactives molecules delivery
Bickoff et al. Stabilization of carotene with nordihydroguaiaretic acid and other antioxidants
Adilah et al. Storage stability of mayonnaise packaged in soy protein isolate films incorporated with mango kernel extract
JPS6170958A (ja) Ｅｐａ強化食品
JP2017135993A (ja) 油脂組成物、かけ油、並びにそれを用いた食品、及び食品の製造方法

Legal Events

Date Code Title Description
AS Assignment

Owner name: KALAMAZOO HOLDINGS, INC., A CORP. OF MI, MICHIGAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:TODD, PAUL H. JR.;REEL/FRAME:005477/0130

Effective date: 19900622

STCF Information on status: patent grant

Free format text: PATENTED CASE

CC Certificate of correction
FPAY Fee payment

Year of fee payment: 4

FPAY Fee payment

Year of fee payment: 8

FPAY Fee payment

Year of fee payment: 12